CN1563494A - Corrosion inhibitor anti corrosion of sulfureted hydrogen - Google Patents
Corrosion inhibitor anti corrosion of sulfureted hydrogen Download PDFInfo
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- CN1563494A CN1563494A CN 200410021473 CN200410021473A CN1563494A CN 1563494 A CN1563494 A CN 1563494A CN 200410021473 CN200410021473 CN 200410021473 CN 200410021473 A CN200410021473 A CN 200410021473A CN 1563494 A CN1563494 A CN 1563494A
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Abstract
A Corrosion inhibitor of anticorrosion to hydrogen sulfide in production, collection and transport media of oil gas field-containing hydrogen sulfide includes alkynyl oxygen group benzyl ammonia chloride and alcohol which can be added with a certain quantity of alkynyl oxygen methyl ammonia imidazoline amide and water according to the needs. This invention can get an organic compound containing triple bond, phen and long bond group in one reaction. Since the compound contains N, O active atomic groups and big pi bonds and easy to adsorb and deposit on metal surface, it can form a complete corrosion inhibition protection film on metal surface.
Description
Technical field
The present invention relates to chemical field, the hydrogen sulfide that is association in the defeated process of a kind of inhibited oil gas-field exploitation, collection is to collecting device corrosive high-efficient corrosion inhibitor.
Background technology
In recent years, the fast development of petroleum industry, will beat several thousand mouthfuls of oil wells every year at least, one of them major issue be exactly in the oil well usually association a large amount of hydrogen sulfide is arranged, and the content of hydrogen sulfide is in rising trend in recent years.We know, hydrogen sulfide is a kind of material with very strong toxicity and corrosion failure, what it caused is that serious hydrogen fracturing is opened and brittle rupture, has extremely strong destructiveness and dangerous, has many about hydrogen sulfide corrosion destructive example report and relevant book information at present both at home and abroad.For this reason, in these years there are many scientific workers to make hard effort for control hydrogen sulfide fragility corrosion failure, also work out many corrosion inhibitor product, but they are the molecule that adopts absorption and complexing action mostly, and it contains the organic compound of N, O, S, carboxyl, sulfydryl and three key.As organic amine, acid amides, tetrahydroglyoxaline, quaternary ammonium salt etc., its corrosion mitigating effect is all not very good.
Summary of the invention
The purpose of this invention is to provide a kind of is the hydrogen sulfide corrosion resistant agent of main component with alkynes oxygen methyl-benzyl ammonium chloride and alkynes oxygen methylamine.
The object of the present invention is achieved like this: it is made up of following component and ratio of weight and number: 30～70 parts of alkynes oxygen methyl-benzyl ammonium chlorides, and weight percent concentration is greater than 30～70 parts of 95% ethanol;
Above-mentioned alkynes oxygen methyl-benzyl ammonium chloride can also be alkynes oxygen methyl-benzyl brometo de amonio; Ethanol can also be methyl alcohol, Virahol and butanols.
Hydrogen sulfide corrosion resistant agent of the present invention also comprises the alkynes oxygen methylamine that adds 1～40 parts by weight.
The present invention can also add the imidazoline amide of 2～30 parts by weight as required; The water that can also add 1～30 parts by weight.
The preferred parts by weight of ethanol that the present invention adds are 40～70 parts.
The inhibiter of hydrogen sulfide corrosion resistant of the present invention is to be the main body composition with alkynes oxygen methylamine, alkynes oxygen methyl-benzyl ammonium chloride, the high-efficient corrosion inhibitor that collaborative imidazoline amide, ethanol equal solvent form.N, O active group had both been contained in its organic compound; contain three key, big π key again; produce chemisorption and physical adsorption easily in the metallic surface; simultaneously also can be by effects such as precipitation and polymerizations; form complete inhibiter protective membrane in the metallic surface, play shielding effect, thereby reduce corrosion of metal speed; performance with better hydrogen sulfide corrosion resistant shows excellent inhibition protection effect.
The molecular formula of the alkynes oxygen methylamine among the present invention is:
R-N(CH
2OCH
2C≡CH)
2
Wherein R is cycloalkyl, aryl, alkyl and substitutive derivative, and carbonatoms is 6～10.Synthetic method is that Paraformaldehyde 96 (or formaldehyde), alkynol are joined in the reactor, heated and stirred is when refluxing, begin to drip organic amine (as hexahydroaniline etc.), the control rate of addition, guarantee in 1.5～3.5 hours, to be added dropwise to complete, stirring reaction 2～3.5 hours between 90～100 ℃ then, cooling discharge promptly gets this product.
The molecular formula of the alkynes oxygen methyl-benzyl ammonium chloride among the present invention is:
Wherein R ' is aryl, alkyl etc., and carbonatoms is 6～10; X is a halogen atom, as Cl
-, Br
-Its synthetic method is that a certain amount of haloalkane and ethanol are joined in the reactor of alkynes oxygen methylamine, between the heated and stirred, 78～88 ℃ of control reaction temperature, reacts 36～45 hours, obtains quarternary ammonium salt compound.
The molecular formula of the imidazoline amide among the present invention is:
R wherein
1Be aryl and alkyl; R
2Be alkyl, aryl etc.
The present invention mixes with multiple dispersion agent, solvent arbitrary proportion, can also contain N compound and quaternary ammonium salt etc. with other and unite use, can further improve the performance of its hydrogen sulfide corrosion resistant, thereby improves its inhibition efficiency greatly.
To be described in further detail invention by example below, but following example only is the present invention's example wherein, the rights protection scope of not representing the present invention and being limited, the scope of the present invention is as the criterion with claims.
Embodiment
Example 1: 30 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 70 kilograms of ethanol (concentration＞95%), this proportioning is low at water ratio, hydrogen sulfide content is during less than 2500mg/L, has that solvability is good, using dosage is low, good effectiveness.
Example 2: 40 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 70 kilograms of ethanol 60 (concentration＞95%), this proportioning have that cost is moderate, consumption is low, produce the ability that all has good hydrogen sulfide corrosion resistant in--collection--defeated Oil, Water, Gas three-phase in the oil field.
Example 3: 70 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 70 kilograms of ethanol 30 (concentration＞95%), it is low that this proportioning has a consumption, at high hydrogen sulfide content such as 3500mg/L, produce the ability that all has good opposing hydrogen sulfide corrosion in--collection--defeated Oil, Water, Gas three-phase in the oil field, just cost is higher.
Example 4: get 40 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 60 kilograms of Virahols (industrial goods), this parts by weight proportioning has that cost is moderate, consumption is low, produce the ability that all has good hydrogen sulfide corrosion resistant in--collection--defeated Oil, Water, Gas three-phase in the oil field, have the cotton-shaped ability of stronger dispersion simultaneously.
Example 5: get 40 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 60 kilograms of these parts by weight proportionings of methyl alcohol (industrial first grade) and have that cost is lower, using dosage is low, produce the ability that has good hydrogen sulfide corrosion resistant in--collection--defeated Oil, Water, Gas three-phase in the oil field.
Example 6: 35 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 5 kilograms of alkynes oxygen methylamine, ethanol 60 (concentration＞95%) kilogram; This parts by weight proportioning has effective, working concentration is low, inject inhibiter at oil well outlet manifold, can produce distribution well in--collection--defeated Oil, Water, Gas three-phase in the oil field, in three-phase with the corrosion of Carbon Steel speed control in ministerial standard index much smaller than 0.076mm/a.Simultaneously, this prescription has the little characteristics of emulsification tendency.
Example 7: 35 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 10 kilograms of imidazoline amides, 55 kilograms of ethanol (concentration＞95%), this parts by weight proportioning is produced in the oil field--collection--fails the ability that all has good hydrogen sulfide corrosion resistant in the Oil, Water, Gas three-phase, but it has strengthened inhibiter in the ratio that water distributes, and more pays attention to the corrosive control of water.
Example 8: the effective content of 10 kilograms of alkynes oxygen methylamine, 30 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 10 kilograms of imidazoline amides, 50 kilograms of ethanol (concentration＞95%), this parts by weight proportioning is higher, (in＞3500mg/L) the output liquid, producing the ability that has better hydrogen sulfide corrosion resistant in--collection--defeated Oil, Water, Gas three-phase in the oil field than high-moisture percentage (＞10%) and higher hydrogen sulfide content.
Example 9: 5 kilograms of alkynes oxygen methylamine, 30 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 10 kilograms of imidazoline amides, 50 kilograms of ethanol (concentration＞95%), 5 kilograms in water, the effective content of this parts by weight proportioning is higher, in oil well and line of pipes (as subsea pipeline), produce the ability that has good hydrogen sulfide corrosion resistant in--collection--defeated Oil, Water, Gas three-phase in the oil field than the high salinity output water of high-moisture percentage (10%～20%).
Example 10: 30 kilograms of alkynes oxygen methyl-benzyl ammonium chlorides, 65 kilograms of ethanol (concentration＞95%), 5 kilograms in water; This parts by weight proportioning is low at water ratio, hydrogen sulfide content is during less than 2500mg/L, has that solvability is good, using dosage is low, good effectiveness.
Example 11: 40 kilograms of alkynes oxygen methyl-benzyl brometo de amonios, ethanol 60 (concentration＞95%) kilogram; This parts by weight proportioning has cost and slightly improves, but its usage quantity is low, produces in the oil field--collection--fails the ability that all has good hydrogen sulfide corrosion resistant in the Oil, Water, Gas three-phase.Simultaneously, also has certain bactericidal property.Example 12: 5 kilograms in 35 kilograms of alkynes oxygen methyl-benzyl brometo de amonios, 10 kilograms of imidazoline amides, ethanol 50 (concentration＞95%) kilogram, water; It is low that this parts by weight proportioning has a consumption, produces the ability that all has good hydrogen sulfide corrosion resistant in--collection--defeated Oil, Water, Gas three-phase in the oil field.Particularly control is long apart from corrosion of gathering line lower aqueous and bacterial corrosion better effects if.
Test conditions:
(1) test(ing) medium: high-salinity brine (salinity 35000mg/L, [Cl
-]=20000mg/L, [HCO
3 -]=1000-4500mg/L, [Ca
2+]=300-500mg/L, pH value 6.5-8.5), H
2S content is 2000-3500mg/L crude oil;
Water: crude oil=8: 2
Testing liquid cumulative volume: 2000 milliliters.
(2) test pressure: with nitrogen pressure to 0.5MPa;
(3) test temperature: 70 ℃;
(4) test period: 24 hours;
(5) test material: N-80 steel;
(6) density of corrosion inhibitor: 20mg/L.
Test-results:
Test-results is listed in the table below.
| Inhibiter | Gas phase | Oil phase | Water | |||
| Corrosion speed (mm/a) | Inhibition efficiency (%) | Corrosion speed (mm/a) | Inhibition efficiency (%) | Corrosion speed (mm/a) | Inhibition efficiency (%) | |
| Example 1 | ???0.0341 | ????71.10 | ??0.0361 | ????67.77 | ??0.0432 | ????71.58 |
| Example 2 | ???0.0302 | ????74.41 | ??0.0340 | ????71.69 | ??0.0413 | ????72.83 |
| Example 3 | ???0.0241 | ????79.58 | ??0.0282 | ????76.52 | ??0.0329 | ????78.36 |
| Example 4 | ???0.0328 | ????72.20 | ??0.0298 | ????75.19 | ??0.0318 | ????79.08 |
| Example 5 | ???0.0282 | ????76.10 | ??0.0321 | ????73.27 | ??0.0331 | ????78.22 |
| Example 6 | ???0.0319 | ????73.00 | ??0.0338 | ????71.86 | ??0.0361 | ????76.25 |
| Example 7 | ???0.0330 | ????72.03 | ??0.0301 | ????74.94 | ??0.0274 | ????81.97 |
| Example 8 | ???0.0324 | ????72.54 | ??0.0291 | ????75.77 | ??0.0285 | ????81.25 |
| Example 9 | ???0.0338 | ????71.36 | ??0.0310 | ????74.19 | ??0.0303 | ????80.07 |
| Example 10 | ???0.0366 | ????68.98 | ??0.0352 | ????70.69 | ??0.0342 | ????77.50 |
| Example 11 | ???0.0305 | ????74.15 | ??0.0288 | ????76.02 | ??0.0374 | ????75.39 |
| Example 12 | ???0.0328 | ????72.20 | ??0.0325 | ????72.94 | ??0.0301 | ????80.20 |
| Blank | ???0.1180 | ????---- | ??0.1201 | ????---- | ??0.1520 | ????---- |
See that from last table in the cited example, under above-mentioned experiment condition, corrosion of Carbon Steel speed is all less than the requirement of the index＜0.076mm/a of oil standard code promulgated by the ministries or commissions of the Central Government.
Claims (5)
1, a kind of inhibiter that is applicable to the hydrogen sulfide corrosion resistant in sulfide hydrogen oil gas real estate, collection, the defeated medium, it is made up of following component and ratio of weight and number: 30～70 parts of alkynes oxygen methyl-benzyl ammonium chlorides, concentration is greater than 30～70 parts of 95% ethanol;
Above-mentioned alkynes oxygen methyl-benzyl ammonium chloride can also be alkynes oxygen methyl-benzyl brometo de amonio; Ethanol can also be methyl alcohol, Virahol and butanols.
2, inhibiter according to claim 1 is characterized in that adding the alkynes oxygen methylamine of 1～40 parts by weight.
3, inhibiter according to claim 1 and 2 is characterized in that adding the imidazoline amide of 2～30 parts by weight.
4, inhibiter according to claim 1, it is characterized in that adding the preferred parts by weight of ethanol is 40～70 parts.
5, inhibiter according to claim 1 is characterized in that adding the water of 1～30 parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100214736A CN1296519C (en) | 2004-03-26 | 2004-03-26 | Corrosion inhibitor anti corrosion of sulfureted hydrogen |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100214736A CN1296519C (en) | 2004-03-26 | 2004-03-26 | Corrosion inhibitor anti corrosion of sulfureted hydrogen |
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| CN1563494A true CN1563494A (en) | 2005-01-12 |
| CN1296519C CN1296519C (en) | 2007-01-24 |
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|---|---|---|---|
| CNB2004100214736A Expired - Fee Related CN1296519C (en) | 2004-03-26 | 2004-03-26 | Corrosion inhibitor anti corrosion of sulfureted hydrogen |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591803C (en) * | 2006-09-04 | 2010-02-24 | 中国石油集团川庆钻探工程有限公司 | Corrosion inhibitor resistant to H2S and CO2 |
| CN101654303B (en) * | 2008-08-18 | 2011-05-04 | 天津大港油田科远石油工程有限责任公司 | Corrosion inhibitor suitable for complex wastewater of oilfield and preparation method thereof |
| CN102517588A (en) * | 2011-12-16 | 2012-06-27 | 中国石油天然气集团公司 | H2S corrosion resistant ground gathering system corrosion inhibitor and preparation method thereof |
| CN101760188B (en) * | 2009-12-31 | 2013-03-13 | 山东德仕化工集团有限公司 | Formula of DSS-1 corrosion inhibiter and processing technique |
| CN104630784A (en) * | 2015-02-09 | 2015-05-20 | 西安华诺石油技术开发有限公司 | Anti-carbon dioxide corrosion inhibitor and preparation method thereof |
| CN106047326A (en) * | 2016-06-03 | 2016-10-26 | 中国石油天然气股份有限公司 | CO2-driving corrosion and scale inhibitor suitable for high-mineralization-degree and high-barium-strontium environment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4026807A (en) * | 1974-08-09 | 1977-05-31 | Petrolite Corporation | Alkynoxymethyl amines |
| US4248796A (en) * | 1978-11-24 | 1981-02-03 | Petrolite Corporation | Quaternary alkynoxymethyl amines |
| CN1086381C (en) * | 1992-06-18 | 2002-06-19 | 中国科学院金属腐蚀与防护研究所 | Preparation process of alkynyl oxy-methylamine and its quaternary amine salt and corrosion buffer agent |
-
2004
- 2004-03-26 CN CNB2004100214736A patent/CN1296519C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100591803C (en) * | 2006-09-04 | 2010-02-24 | 中国石油集团川庆钻探工程有限公司 | Corrosion inhibitor resistant to H2S and CO2 |
| CN101654303B (en) * | 2008-08-18 | 2011-05-04 | 天津大港油田科远石油工程有限责任公司 | Corrosion inhibitor suitable for complex wastewater of oilfield and preparation method thereof |
| CN101760188B (en) * | 2009-12-31 | 2013-03-13 | 山东德仕化工集团有限公司 | Formula of DSS-1 corrosion inhibiter and processing technique |
| CN102517588A (en) * | 2011-12-16 | 2012-06-27 | 中国石油天然气集团公司 | H2S corrosion resistant ground gathering system corrosion inhibitor and preparation method thereof |
| CN102517588B (en) * | 2011-12-16 | 2013-10-16 | 中国石油天然气集团公司 | H2S corrosion resistant ground gathering system corrosion inhibitor and preparation method thereof |
| CN104630784A (en) * | 2015-02-09 | 2015-05-20 | 西安华诺石油技术开发有限公司 | Anti-carbon dioxide corrosion inhibitor and preparation method thereof |
| CN106047326A (en) * | 2016-06-03 | 2016-10-26 | 中国石油天然气股份有限公司 | CO2-driving corrosion and scale inhibitor suitable for high-mineralization-degree and high-barium-strontium environment |
| CN106047326B (en) * | 2016-06-03 | 2019-06-11 | 中国石油天然气股份有限公司 | It is a kind of suitable for high salinity, the CO of high barium strontium environment2Drive corrosion inhibiting and descaling agent |
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|---|---|
| CN1296519C (en) | 2007-01-24 |
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